EP3508592A1 - Procédé de récupération de scandium - Google Patents

Procédé de récupération de scandium Download PDF

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Publication number
EP3508592A1
EP3508592A1 EP17846190.1A EP17846190A EP3508592A1 EP 3508592 A1 EP3508592 A1 EP 3508592A1 EP 17846190 A EP17846190 A EP 17846190A EP 3508592 A1 EP3508592 A1 EP 3508592A1
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Prior art keywords
scandium
solution
oxalate
treatment
oxalic acid
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EP17846190.1A
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German (de)
English (en)
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EP3508592A4 (fr
Inventor
Tatsuya Higaki
Masaki Imamura
Osamu Nakai
Hiroshi Kobayashi
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Sumitomo Metal Mining Co Ltd
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Sumitomo Metal Mining Co Ltd
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Publication of EP3508592A1 publication Critical patent/EP3508592A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/20—Compounds containing only rare earth metals as the metal element
    • C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
    • C01F17/212—Scandium oxides or hydroxides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F17/00—Compounds of rare earth metals
    • C01F17/10—Preparation or treatment, e.g. separation or purification
    • C01F17/13—Preparation or treatment, e.g. separation or purification by using ion exchange resins, e.g. chelate resins
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B59/00—Obtaining rare earth metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present invention relates to a method for recovering scandium. Specifically, the present invention relates to a method for recovering scandium in the form of scandium oxide by subjecting a solution containing scandium to an oxalate conversion treatment and roasting scandium oxalate thus obtained.
  • HPAL high pressure acid leaching
  • a method for recovering scandium from the acidic solution after addition of sulfurizing agent described above as scandium oxide by, for example, an ion exchange (IX) method, a solvent extraction method, an oxalate conversion and precipitation method, and a roasting method.
  • IX ion exchange
  • Scandium is extremely useful as an additive for a high strength alloy and an electrode material for a fuel cell, is expected to be widely used in various fields in the future, and is thus required to be efficiently recovered.
  • Patent Document 1 Japanese Unexamined Patent Application, Publication No. 2014-218719
  • An object of the present invention is to provide a method for recovering scandium as scandium oxide which contains scandium at a high content and is in the form of coarse particles having favorable handling property.
  • the present inventors have conducted extensive studies to solve the aforementioned problems. As a result, the present inventors have found out that it is possible to promote the crystal growth of scandium oxalate to be obtained by adjusting the temperature of the reaction solution during the treatment to a predetermined range when generating scandium oxalate by subjecting a scandium-containing solution to an oxalate conversion treatment. Then the present invention has been completed.
  • the method for recovering scandium according to the present embodiment is a method for recovering scandium from an acidic solution containing scandium and an impurity component.
  • this method for recovering scandium is a method which includes a step for carrying out an oxalate conversion treatment in which oxalic acid is used in a solution containing scandium and an impurity component (hereinafter also referred to as the "scandium-containing solution") to cause a reaction in which the scandium is converted into an oxalate form.
  • scandium oxalate to be obtained by performing such an oxalate conversion treatment can be converted into the form of scandium oxide by being roasted.
  • a solution obtained by subjecting a leachate obtained by the high pressure acid leaching (HPAL) treatment of nickel oxide ore to a sulfuration treatment to separate nickel therefrom and subjecting the post-sulfuration liquid thus obtained to an ion exchange treatment and/or a solvent extraction treatment to separate impurities therefrom and enrich scandium therein can be used.
  • HPAL high pressure acid leaching
  • scandium can be left in the solution while nickel is converted into a sulfide by a sulfuration treatment in the HPAL process and nickel and scandium can be thus effectively separated from each other.
  • the temperature of the reaction solution during the treatment is adjusted to a predetermined range upon such an oxalate conversion treatment of a scandium-containing solution using oxalic acid.
  • This makes it possible to promote the crystal growth of scandium oxalate to be obtained and to obtain scandium oxalate having a large particle diameter.
  • by roasting the scandium oxalate obtained it is possible to obtain scandium oxide coarsened to a desired particle diameter and to improve the handling property as well as it is possible to obtain scandium oxide containing scandium at a high content.
  • a solution obtained by separating nickel from a leachate obtained by the high pressure acid leaching (HPAL) treatment of nickel oxide ore as a sulfide and subjecting the solution thus obtained to an ion exchange treatment and a solvent extraction treatment to remove impurity components therefrom can be used as the solution containing scandium and impurity components such as iron (scandium-containing solution).
  • HPAL high pressure acid leaching
  • Fig. 1 is a flow diagram for illustrating the flow of a hydrometallurgy process of nickel oxide ore.
  • the hydrometallurgy process of nickel oxide ore includes a leaching step S11 of leaching nickel oxide ore with sulfuric acid under high temperature and high pressure to obtain a leach slurry; a solid-liquid separation step S12 of performing solid-liquid separation to separate the leach slurry into a leachate and a leach residue; a neutralization step S13 of adding a neutralizing agent to the leachate to obtain a neutralized precipitate containing impurities and a post-neutralization liquid; and a sulfuration step S14 of adding a sulfurizing agent to the post-neutralization liquid to obtain nickel sulfide and a post-sulfuration liquid.
  • the leaching step S11 is a step for adding sulfuric acid to a slurry of nickel oxide ore, for example, in a high temperature pressurized vessel (an autoclave) and the like, supplying high pressure steam and high pressure air into the vessel, and stirring the slurry at a temperature of 240°C to 260°C to generate a leach slurry containing a leachate containing nickel and a leach residue containing hematite. Note that scandium is contained in the leachate together with nickel.
  • examples of nickel oxide ore mainly include so-called laterite ore such as limonite ore and saprolite ore.
  • the content of nickel in laterite ore is usually 0.8 to 2.5 wt%, and nickel is contained as a hydroxide or a silica magnesia (magnesium silicate) mineral.
  • these types of nickel oxide ore contain scandium.
  • the solid-liquid separation step S12 is a step for performing solid-liquid separation of the leach slurry generated in the leaching step S11 described above into a leachate containing nickel and cobalt and the leach residue of hematite by multi-stage washing.
  • the leach slurry is mixed with a washing liquid, and then solid-liquid separation is performed by using a solid-liquid separation apparatus such as a thickener. Specifically, the leach slurry is first diluted with the washing liquid, and then the leach residue in the slurry is condensed as a precipitate in the thickener. This makes it possible to decrease the amount of nickel attached to the leach residue according to the degree of dilution. In actual operation, thickeners having such a function are used by being connected in multiple stages.
  • the neutralization step S13 is a step for adding a neutralizing agent to the leachate to adjust the pH, thereby obtaining a neutralized precipitate containing impurity elements and a post-neutralization liquid.
  • the neutralizing agent in the neutralization step S13, publicly known substances can be used as the neutralizing agent and examples thereof may include limestone, slaked lime, and sodium hydroxide.
  • the pH is preferably adjusted to the range of 1 to 4 and more preferably to the range of 1.5 to 2.5 while suppressing oxidation of the leachate separated.
  • the pH is less than 1, neutralization may be insufficient, and the neutralized precipitate and the post-neutralization liquid may not be separated.
  • the pH when the pH is more than 4, not only impurities including aluminum but also valuable metals such as scandium and nickel may be contained in the neutralized precipitate.
  • the sulfuration step S14 is a step for adding a sulfurizing agent to the post-neutralization liquid obtained in the neutralization step S13 described above to obtain nickel sulfide and a post-sulfuration liquid.
  • Nickel, cobalt, zinc, and the like are recovered as sulfides and scandium and the like remain in the post-sulfuration liquid by the sulfuration treatment in this sulfuration step S14.
  • nickel and scandium can be effectively separated from each other by the sulfuration treatment in this hydrometallurgy process of nickel oxide ore.
  • a sulfurizing agent such as gaseous hydrogen sulfide, sodium sulfide, or hydrogenated sodium sulfide is blown into the post-neutralization liquid obtained to generate a sulfide containing nickel (nickel sulfide) with less impurity components and a post-sulfuration liquid which has a low and stabilized level of nickel concentration and contains scandium and the like.
  • the separation treatment of a slurry of nickel sulfide is performed using a sedimentation apparatus such as a thickener to separate and recover nickel sulfide from the bottom of the thickener. Meanwhile, the post-sulfuration liquid of an aqueous solution component is allowed to overflow for recovery.
  • a solution obtained by recovering the post-sulfuration liquid of an acidic solution of sulfuric acid obtained through each step in the hydrometallurgy process of nickel oxide ore as described above and subjecting the post-sulfuration liquid to an ion exchange treatment and a solvent extraction treatment to be described later can be used as a starting material, and scandium oxide is generated from this solution.
  • a solution obtained by subjecting the post-sulfuration liquid obtained through the sulfuration step in the hydrometallurgy process of nickel oxide ore to an ion exchange treatment and a solvent extraction treatment can be used as the scandium-containing solution. It is possible to separate and remove impurities in the solution and enrich scandium by subjecting the post-sulfuration liquid to an ion exchange treatment and/or a solvent extraction treatment in this way.
  • each of the ion exchange treatment and the solvent extraction treatment will be described. Note that the solvent extraction treatment is described by taking an aspect in which an eluate obtained through the ion exchange treatment is subjected to the solvent extraction treatment as an example, but only the solvent extraction treatment may be performed without performing the ion exchange treatment.
  • the post-sulfuration liquid contains aluminum, chromium, and the like as impurities. Accordingly, it is preferable to remove these impurities and to enrich scandium when recovering scandium in the solution as scandium oxide.
  • Examples of the method for enriching scandium may include a method by an ion exchange treatment using a chelating resin.
  • Fig. 2 is a flow diagram for illustrating an example of the flow of an ion exchange treatment performed by an ion exchange reaction using a chelating resin. Note that the flow until the scandium eluate obtained by the ion exchange treatment is subjected to the solvent extraction treatment is also illustrated in this Fig. 2 .
  • the post-sulfuration liquid obtained through the sulfuration step S14 ( Fig. 1 ) in the hydrometallurgy process of nickel oxide ore is brought into contact with a chelating resin to adsorb scandium in the post-sulfuration liquid onto the chelating resin and to obtain a scandium (Sc) eluate.
  • examples of the ion exchange treatment may include a treatment including: an adsorption step S21 of bringing the post-sulfuration liquid into contact with a chelating resin to adsorb scandium onto the chelating resin; an aluminum removing step S22 of bringing sulfuric acid into contact with the chelating resin to remove aluminum adsorbed on the chelating resin; a scandium elution step S23 of bringing sulfuric acid into contact with the chelating resin which has been subjected to the aluminum removing step S22 to obtain a scandium eluate; and a chromium removing step S24 of bringing sulfuric acid into contact with the chelating resin which has been subjected to the scandium elution step S23 to remove chromium which has been adsorbed onto the chelating resin in the adsorption step S21.
  • the post-sulfuration liquid is brought into contact with a chelating resin to adsorb scandium onto the chelating resin.
  • a chelating resin there is no particular limitation for the kind of the chelating resin, and for example, a resin having iminodiacetic acid as a functional group can be used.
  • the aluminum removing step S22 0.1 N or less of sulfuric acid is brought into contact with the chelating resin which has adsorbed scandium in the adsorption step S21 to remove aluminum adsorbed on the chelating resin.
  • the pH is preferably maintained in the range of between 1 or more and 2.5 or less and more preferably maintained in the range of between 1.5 or more and 2.0 or less.
  • the scandium elution step S23 0.3 N or more and less than 3 N of sulfuric acid is brought into contact with the chelating resin which has been subjected to the aluminum removing step S22 to obtain a scandium eluate.
  • the normality of sulfuric acid used as an eluent is preferably maintained in the range of between 0.3 N or more and less than 3 N, and more preferably maintained in the range of between 0.5 N or more and less than 2 N.
  • the chromium removing step S24 3 N or more of sulfuric acid is brought into contact with the chelating resin which has been subjected to the scandium elution step S23 to remove chromium adsorbed on the chelating resin. It is not preferable that the normality of sulfuric acid used as an eluent is less than 3 N when removing chromium since chromium is not properly removed from the chelating resin.
  • the scandium (Sc) eluate obtained through the ion exchange treatment described above is brought into contact with a predetermined extractant to extract scandium.
  • the extractant there is no particular limitation for the extractant to be used in the solvent extraction, and an amine-based extractant, a phosphoric acid-based extractant, and the like can be used.
  • the extractant it is possible to extract scandium of a target for extraction into the organic solvent containing the extractant or it is also possible to selectively extract impurity components into the extractant and to leave scandium in the raffinate liquid.
  • impurity components are selectively extracted into the organic solvent and scandium is contained and enriched in the raffinate liquid since an amine-based extractant is an extractant having low selectivity for scandium.
  • each step of the solvent extraction treatment may include a treatment including: an extraction step S31 of mixing the scandium eluate with an extractant and separating the mixture into a post-extraction organic solvent into which impurities have been extracted and a raffinate liquid containing scandium; a scrubbing step S32 of mixing the post-extraction organic solvent with a hydrochloric acid solution or a sulfuric acid solution to separate scandium which is contained in the post-extraction organic solvent in a trace amount; and a backward extraction step S33 of mixing the post-washing organic solvent with a backward extraction starting liquid to perform backward extraction of impurities from the post-washing organic solvent and to obtain a backward extraction liquid.
  • a treatment including: an extraction step S31 of mixing the scandium eluate with an extractant and separating the mixture into a post-extraction organic solvent into which impurities have been extracted and a raffinate liquid containing scandium; a scrubbing step S32 of mixing the post-extraction organic solvent with a
  • a scandium-containing solution is mixed with an organic solvent containing an extractant and impurities are selectively extracted into the organic solvent to obtain an organic solvent containing the impurities and a raffinate liquid in which scandium is enriched.
  • an amine-based extractant for example, an amine-based extractant is used.
  • the amine-based extractant it is possible to use amine-based extractants known under trade names of PrimeneJM-T which is a primary amine, LA-1 which is a secondary amine, tri-n-octylamine (TNOA) and tri-i-octylamine (TIOA) which are a tertiary amine.
  • PrimeneJM-T which is a primary amine
  • LA-1 which is a secondary amine
  • TNOA tri-n-octylamine
  • TIOA tri-i-octylamine
  • the extractant such as an amine-based extractant is diluted with, for example, a hydrocarbon-based organic solvent and used.
  • concentration of extractant in the organic solvent it is preferably about 1 vol% or more and 10 vol% or less and particularly preferably about 5 vol% in consideration of phase separation property at the time of extraction and at the time of backward extraction to be described later.
  • volume proportion of the organic solvent to the scandium-containing solution at the time of extraction but it is preferable to set the molar quantity of the organic solvent to about 0.01 times or more and 0.1 times or less the molar quantity of metals in the scandium-containing solution.
  • the extraction step S31 described above in a case in which scandium slightly coexists in the organic solvent into which impurities have been extracted from the scandium-containing solution, it is preferable to subject the organic solvent (organic phase) to a scrubbing (washing) treatment to separate scandium into the aqueous phase and to recover the scandium from the extractant prior to the backward extraction of the extraction liquid obtained in the extraction step S31 (scrubbing step S32).
  • scrubbing step S32 By providing the scrubbing step S32 and thus washing the organic solvent and separating a small amount of scandium extracted by the extractant in this way, it is possible to separate scandium into the washing liquid and to further increase the recovery rate of scandium.
  • washing solution As a solution (washing solution) to be used in scrubbing, a sulfuric acid solution, a hydrochloric acid solution, and the like can be used. It is also possible to use one into which a water-soluble chloride or sulfate is added. Specifically, when a sulfuric acid solution is used as the washing solution, it is preferable to use one having a concentration in the range of between 1.0 mol/L or more and 3.0 mol/L or less.
  • the number of washing stages also depends on the kind and concentration of impurity elements and it can be thus appropriately changed depending on the respective extractants and the extraction conditions. For example, in a case in which the phase ratio O/A of the organic phase (O) to the aqueous phase (A) is set to 1, it is possible to separate scandium extracted into the organic solvent down to a value less than the lower limit value detected by the analyzer by setting the number of stages to about 3 to 5 stages.
  • the impurities are backward-extracted from the organic solvent into which the impurities have been extracted in the extraction step S31.
  • the backward extraction solution (the backward extraction starting liquid) is added to and mixed with an organic solvent containing an extractant to cause a reaction opposite to that for the extraction treatment in the extraction step S31 and thus to backward-extract the impurities and to obtain a post-backward extraction liquid containing the impurities.
  • the concentration of the solution containing a carbonate of the backward extraction solution is, for example, about 0.5 mol/L or more and 2 mol/L or less.
  • the backward extraction treatment can be performed in the same manner by adding the backward extraction solution to the extractant after scrubbing and mixing these together in a case in which the organic solvent containing an extractant has been subjected to the scrubbing treatment in the scrubbing step S32 described above.
  • the extractant obtained by adding a solution of a carbonate such as sodium carbonate to the extractant after extraction or the extractant after scrubbing, performing the backward extraction treatment, and thus separating the impurities from the extractant in this way can be repeatedly used as an extractant to be used in the extraction treatment in the extraction step S31.
  • the scandium-containing solution which is a backward extract obtained through the solvent extraction treatment described above, is subjected to an oxalate conversion treatment to convert scandium into an oxalate salt (scandium oxalate).
  • an oxalate conversion treatment to convert scandium into an oxalate salt (scandium oxalate).
  • oxalic acid is added to the scandium-containing solution to generate and precipitate a solid crystal of scandium oxalate based on scandium in the scandium-containing solution.
  • the oxalic acid to be used may be a solid or a solution.
  • a method of oxalate conversion treatment it is possible to use a method in which a scandium-containing solution is gradually added into an oxalic acid solution filled in a reaction vessel to generate and precipitate a solid crystal of scandium oxalate. At this time, it is preferable to adjust the pH of the scandium-containing solution to a range of between -0.5 or more and 1 or less prior to the oxalate conversion treatment. According to such a method of oxalate conversion treatment, it is possible to prevent precipitation of iron(II) oxalate and the like and it is also possible to recover scandium having a higher purity without using an expensive oxidizing agent and the like.
  • the temperature of the reaction solution during the treatment is adjusted to the range of between 50°C or more and 80°C or less upon the oxalate conversion treatment described above.
  • the temperature of the solution is adjusted preferably to the range of between 55°C or more and 70°C or less and more preferably to 60°C.
  • the oxalate conversion treatment includes a temperature adjusting step S41 of adjusting the temperature of the scandium-containing solution to a specific temperature range, namely, the range of between 50°C or more and 80°C or less and a crystallization step S42 of subjecting the solution (oxalate conversion starting liquid) having a temperature adjusted to an oxalate conversion treatment using oxalic acid to cause precipitation of an oxalate of scandium.
  • the crystals of scandium oxalate obtained are recovered through a filtration and washing step S43 to perform a filtration and washing treatment.
  • the temperature of the scandium-containing solution to be subjected to the oxalate conversion treatment is adjusted to the range of between 50°C or more and 80°C or less, preferably to the range of between 55°C or more and 70°C or less, and more preferably to 60°C.
  • the temperature of the scandium-containing solution can be adjusted by using a heater and the like.
  • an oxalate conversion treatment in which oxalic acid is used in the scandium-containing solution (oxalate conversion starting liquid), of which the temperature has been adjusted to and maintained in the range of between 50°C or more and 80°C or less is carried out to cause a reaction in which the scandium is converted into an oxalate form, and an oxalate of scandium (crystal of scandium oxalate) is obtained.
  • the reaction of oxalate conversion is caused by putting the temperature of the reaction solution during the treatment in a state of between 50°C or more and 80°C or less in this way. This makes it possible to accelerate the crystal growth of scandium oxalate and to coarsen the particles.
  • the temperature of the reaction solution during the treatment is less than 50°C, the crystal growth slows down and the particles do not sufficiently grow to particles having favorable handling property and cannot be thus coarsened.
  • the temperature of the reaction solution during the treatment exceeds 80°C since the particles cannot be coarsened any more but rather the required energy cost, facility cost, and the like increase.
  • the oxalic acid to be used may be a solid or a solution (oxalic acid solution).
  • an oxalic acid solution may be added to the scandium-containing solution to generate crystals of scandium oxalate or an oxalic acid solution may be placed in a reaction vessel and the scandium-containing solution may be added thereto to generate crystals as described above.
  • oxalic acid solution oxalic acid solution
  • a solution of which the temperature has been adjusted to the range of between 50°C or more and 80°C or less in the same manner as the scandium-containing solution.
  • oxalic acid in an amount to be in the range of 1.05 times to 1.2 times the equivalent amount required to precipitate scandium in the scandium-containing solution as an oxalate.
  • the amount of oxalic acid used is less than 1.05 times the equivalent amount required, there is a possibility that the entire amount of scandium cannot be effectively recovered.
  • the amount of oxalic acid used exceeds 1.2 times the equivalent amount required since scandium is redissolved and the recovery rate thereof decreases by an increase in the solubility of scandium oxalate and the amount of oxidizing agent such as sodium hypochlorite used increases in order to decompose excessive oxalic acid.
  • a solution of which the pH has been adjusted to the range of between -0.5 or more and 1 or less.
  • the scandium-containing solution of which the pH has been adjusted to the range of between -0.5 or more and 1 or less it is possible to lower the content of impurities and to recover high purity scandium by adjusting the pH of the oxalic acid solution also to the same range.
  • the present invention is not limited thereto, and it is only required that the temperature of the reaction solution when the scandium-containing solution is mixed with oxalic acid and a reaction is thus caused is maintained in the range of between 50°C or more and 80°C or less.
  • the crystals of scandium oxalate obtained by performing the oxalate conversion treatment as described above are converted into scandium oxide by roasting.
  • the roasting treatment is a treatment in which the crystals of scandium oxalate obtained by the oxalate conversion treatment are washed with water, dried, and then roasted. It is possible to recover scandium as scandium oxide through this roasting treatment. Particularly, in the present embodiment, it is possible to lower the content of impurities in scandium oxalate to be generated and to grow the crystals to a desired size since the temperature of the reaction solution during the treatment is adjusted to and maintained in a predetermined range in the oxalate conversion treatment described above. Moreover, this makes it possible to effectively coarsen the particle diameter of scandium oxide to be obtained through roasting. Hence, it is possible to obtain scandium oxide which contains scandium at a high content and has improved handling property.
  • roasting treatment there is no particular limitation for the conditions of the roasting treatment, but for example, scandium oxalate may be placed in a tubular furnace and heated at about 900°C for about 2 hours.
  • a continuous furnace such as a rotary kiln is preferably used for industrial production since both drying and roasting can be performed by using the same equipment.
  • Nickel oxide ore was leached with sulfuric acid by using an autoclave, and slaked lime was added to the leachate obtained to neutralize the leachate. Subsequently, a sulfurizing agent was added to the post-neutralization liquid obtained to cause a sulfuration reaction, nickel, cobalt and the like were separated from the post-neutralization liquid as sulfides, and a post-sulfuration liquid containing scandium was obtained.
  • the post-sulfuration liquid obtained was subjected to an ion exchange treatment using a chelating resin and thus an eluate (scandium eluate) containing scandium eluted from the chelating resin was obtained as well as impurities in the solution were separated. Thereafter, a neutralizing agent was added to the scandium eluate to generate a precipitate of scandium hydroxide.
  • scandium solution sulfuric acid was added to the precipitate of scandium hydroxide and the precipitate was redissolved to obtain a solution (scandium solution), this scandium solution was subjected to a solvent extraction treatment using an amine-based extractant, and thus a scandium sulfate solution was obtained as a raffinate liquid.
  • the scandium sulfate solution was diluted by adding water to the scandium sulfate solution so that the scandium concentration contained in the solution was about 5 g/L.
  • the pH of the solution was adjusted to and maintained at around 1 by adding sulfuric acid thereto. Note that there was no difference in the particle diameter of the purified products to be obtained in the pH range of about 0 to 1.
  • the oxalate conversion starting liquid was taken by 1.3 liters per one test condition.
  • a solution containing oxalic acid at a concentration of 100 g/L was prepared by 0.54 liters per one test condition. Note that the amount of this oxalic acid solution corresponds to the amount of oxalic acid added to be 2.7 equivalence of scandium contained in the oxalate conversion starting liquid.
  • the average particle diameter (D90) of scandium oxide generated is a size of 29 ⁇ m to 32 ⁇ m.
  • a hydrometallurgy process of nickel oxide ore was performed in the same manner as in Example 1 and then an ion exchange treatment and a solvent extraction treatment were performed to obtain a scandium sulfate solution.
  • the scandium concentration of the scandium sulfate solution obtained was adjusted to 10 g/L and the pH thereof was adjusted to 0 with sulfuric acid. This solution was used as an oxalate conversion starting liquid.
  • the oxalate conversion starting liquid was taken by 1.3 liters per one test condition.
  • a solution containing oxalic acid at a concentration of 100 g/L was prepared by 0.54 liters per one test condition. Note that the amount of this oxalic acid solution corresponds to the amount of oxalic acid added to be 2.7 equivalence of scandium contained in the oxalate conversion starting liquid.
  • Example 2 the temperatures of the oxalate conversion starting liquid and the oxalic acid solution were each raised to and maintained at 60°C.
  • the oxalate conversion treatment was performed using these solutions by two methods of a method (Example 2-1) in which the oxalate conversion starting liquid was added into the oxalic acid solution to form an oxalate and a method (Example 2-2) in which the oxalic acid solution was added into the oxalate conversion starting liquid to form an oxalate as presented in the following Table 3.
  • the oxalate conversion starting liquid was added into the oxalic acid solution contained in the reaction vessel at a flow rate of about 0.5 L/min while stirring the oxalic acid solution.
  • the oxalic acid solution was added into the oxalate conversion starting liquid at a flow rate of about 0.5 L/min while stirring the oxalate conversion starting liquid. Note that the temperature of the reaction solution during the treatment was maintained at 60°C.
  • the average particle diameter (D90) of scandium oxide generated is a size of 25 ⁇ m to 27 ⁇ m and it has been confirmed that there is no difference in the particle diameter depending on the method of oxalate conversion treatment.
  • a hydrometallurgy process of nickel oxide ore was performed in the same manner as in Example 1 and then an ion exchange treatment and a solvent extraction treatment were performed to obtain a scandium sulfate solution.
  • the scandium concentration of the scandium sulfate solution obtained was adjusted to 10 g/L and the pH thereof was adjusted to 0 with sulfuric acid. This solution was used as an oxalate conversion starting liquid.
  • the oxalate conversion starting liquid was taken by 1.3 liters per one test condition.
  • a solution containing oxalic acid at a concentration of 100 g/L was prepared by 0.54 liters per one test condition. Note that the amount of this oxalic acid solution corresponds to the amount of oxalic acid added to be 2.7 equivalence of scandium contained in the oxalate conversion starting liquid.
  • Comparative Example 1 the oxalate conversion starting liquid and the oxalic acid solution were each divided into two portions so that those of which the temperature was maintained at a temperature condition of room temperature (25°C) (Comparative Example 1-1) and those of which the temperature was raised to and maintained at 40°C (Comparative Example 1-2) were prepared. Using these solutions, the oxalate conversion starting liquid was added into the oxalic acid solution contained in the reaction vessel at a flow rate of about 0.5 L/min while stirring the oxalic acid solution. Note that the conditions of the oxalate conversion treatment are summarized in the following Table 5.
  • the stirring state was continuously maintained for 30 minutes to 120 minutes. Subsequently, the entire amount of the resultant mixture was filtered for solid-liquid separation, and the crystals of scandium oxalate separated were subjected to repulp washing with pure water in an amount of 50 g/L three times.

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